EP0659745B1 - Substituted 1-aryl pyrazoles - Google Patents

Abstract

1-(Phenyl or pyridyl)-4-(trifluoroethylthio, -sulfinyl or -sulfonyl)-pyrazole derivatives (I) are new. Pyrazole derivatives of formula (I) are new. R1 = H, CN, 1-6C alkyl, (1-4C) alkoxy-(1-4C) alkyl, 1-4C haloalkyl or cyano-(1-2C) alkyl; R2 = trifluoroethyl; R3 = H, NH2, halo, -NHCOR4, -N=C(R5)-NR5R6, 1H-pyrrol-1-yl, -N=CR5R6 or -N=C(R5)-OR7; R4 = 1-6C alkyl (optionally substituted by 1-3 halo), (1-6C) alkoxy-(1-6C) alkyl or phenyl (optionally mono-, di- or trisubstituted); R5 = H or 1-6C alkyl; R6 = H, 1-6C alkyl or phenyl (optionally mono-, di- or trisubstituted); or CR5R6 = optionally substituted pyridyl; R7 = 1-6C alkyl; Ar = phenyl or pyridyl (both optionally substituted by 1-3 of halo, 1-6C haloalkyl, 1-6C haloalkylthio, 1-6C haloalkoxy, alkoxy, hydrazino, di-(1-6C alkyl)-hydrazino, NH2, 1-6C mono- or diaminoalkyl, 1-6C iminoalkyl, CN, 1-6C alkylthio or -CONR9R10); R9, R10 = H or alkyl; and n = 0-2. AN Independent claim is also included for the preparation of (I).

Description

The invention relates to novel substituted 1-arylpyrazoles, several processes for theirs Production and their use as pesticides.

It is already known that certain substituted 1-arylpyrazoles, such as 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3-cyano-4 - [(trifluoromethyl) sulfinyl] -1H-pyrazole have a good activity against pests (see. e.g. EP-A 295 117 and EP-A 352 944).

Furthermore, numerous substituted 1-arylpyrazoles are described which are used for controlling can be used by pests (see for example EP-A 201 852, EP-A 418 016).

In addition, substituted 1-arylpyrazoles also serve as intermediates for the production of pesticides (see for example EP-A 301 338, EP-A 301 339, EP-A 374 061, EP-A 260 521).

However, the effective amount or duration of action of the previously known compounds is, in particular in certain insects or at low application levels not completely satisfactory in all fields of application.

in welcher

R¹

für Wasserstoff, Cyano, (C₁-C₄)-Alkyl, Methoxymethyl, Ethoxymethyl, Methoxyethyl, Ethoxyethyl, Trifluormethyl, Brommethyl und Cyanomethyl steht,

R²

für 1,1-Difluorethyl steht,

R³

für Amino oder für die folgende Gruppierung steht

wobei

R⁵

für Wasserstoff oder (C₁-C₄)-Alkyl steht und

R⁶

für Phenyl steht,

Ar

für zweifach oder dreifach, gleich oder verschieden substituiertes Phenyl steht, wobei in der 2-Position Fluor oder Chlor, in der 4-Position Trifluormethyl und in der 6-Position Fluor, Chlor, Cyano, Methoxy, Methylthio, Trifluormethyl, Trifluormethoxy, Trifluormethylthio steht oder

Ar

für einen 2-Pyridyl-Rest steht, welcher in 5-Position durch Trifluormethyl und in 3-Position durch Fluor oder Chlor substituiert ist und

n

für eine Zahl 0, 1 oder 2 steht,

gefunden. There have now been new substituted 1-arylpyrazoles of the general formula (I)

in which

R ¹

is hydrogen, cyano, (C ₁ -C ₄ ) -alkyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, trifluoromethyl, bromomethyl and cyanomethyl,

R ²

represents 1,1-difluoroethyl,

R ³

stands for amino or for the following grouping

in which

R ⁵

is hydrogen or (C ₁ -C ₄ ) -alkyl and

R ⁶

stands for phenyl,

Ar

is phenyl substituted twice or three times, identically or differently, in the 2-position fluorine or chlorine, in the 4-position trifluoromethyl and in the 6-position fluorine, chlorine, cyano, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio or

Ar

is a 2-pyridyl radical which is substituted in the 5-position by trifluoromethyl and in the 3-position by fluorine or chlorine, and

n

is a number 0, 1 or 2,

found.

a) Man erhält substituierte 1-Aryl-4-mercapto-pyrazole der Formel (Ia),

in welcher

R¹, R² und Ar

die oben angegebene Bedeutung haben und

R^3-1

für Amino steht,

wenn man
Pyrazolderivate der Formel (II),

in welcher
R¹, R^3-1 und Ar die oben angegebenen Bedeutungen haben,
mit Sulfenylhalogeniden der Formel (III) R²-S-Hal in welcher

R²

die oben angegebene Bedeutung hat und

Hal

für Halogen, insbesondere Chlor oder Brom steht,

gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Reaktionshilfsmittels umsetzt.

b) Man erhält substituierte 1-Arylpyrazole der Formel (Ib),

in welcher

R¹, R², R^3-1 und Ar

die oben angegebenen Bedeutungen haben und

n

für die Zahl 1 oder 2 steht,

wenn man Verbindungen der Formel (Ia)

in welcher
R¹, R², R^3-1 und Ar die oben angegebenen Bedeutungen haben
mit Oxidationsmitteln gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Katalysators oxidiert. Beispielhaft, aber nicht beschränkend sind weitere Herstellungsmethoden für die erfindungsgemäßen Verbindungen der Formel (I) nachstehend aufgeführt, wobei R¹, R², R⁵, R⁶, Ar und n die oben angegebene Bedeutung haben:

c) Umsetzung von substituierten 1-Arylpyrazolen der Formel (Ic) (R^3-1 = NH₂) mit Aldehyden oder Ketonen der Formel (VII)

i) Umsetzung von substituierten 1-Arylpyrazolen der Formel (Ic) (R^3-1 = NH₂) mit Nukleophilen NU

Furthermore, it has been found that the novel substituted 1-arylpyrazoles of the general formula (I) are obtained by one of the processes described below:

a) substituted 1-aryl-4-mercapto-pyrazoles of the formula (Ia) are obtained,

in which

R ¹ , R ² and Ar

have the meaning given above and

R ^3-1

stands for amino,

if
Pyrazole derivatives of the formula (II),

in which
R ¹ , R ^3-1 and Ar have the meanings given above,
with sulfenyl halides of the formula (III) R ² -S-Hal in which

R ²

has the meaning given above and

Hal

is halogen, in particular chlorine or bromine,

if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

b) substituted 1-arylpyrazoles of the formula (Ib) are obtained

in which

R ¹ , R ² , R ^3-1 and Ar

have the meanings given above and

n

stands for the number 1 or 2,

when compounds of the formula (Ia)

in which
R ¹ , R ² , R ^3-1 and Ar have the meanings given above
optionally oxidized with oxidizing agents in the presence of a diluent and optionally in the presence of a catalyst. By way of example, but not by way of limitation, further preparation methods for the compounds of the formula (I) according to the invention are listed below, where R ¹ , R ² , R ⁵ , R ⁶ , Ar and n have the abovementioned meaning:

c) Reaction of substituted 1-arylpyrazoles of the formula (Ic) (R ^3-1 = NH ₂ ) with aldehydes or ketones of the formula (VII)

i) Reaction of substituted 1-arylpyrazoles of the formula (Ic) (R ^3-1 = NH ₂ ) with nucleophiles NU

The general or preferred definitions listed above apply both to the end products of the formula (I) and also to the respective starting or intermediate products required for the preparation. The Definitions can be between each other, including between the specified preferred Area can be combined arbitrarily.

The hydrocarbon radicals mentioned in the remainder definition, such as alkyl, alkoxy, Alkoxyalkyl, alkylthio are also, unless expressly stated, straight-chain or branched.

Halogen is generally fluorine, chlorine, bromine or iodine, preferably Fluorine, chlorine or bromine, in particular for fluorine or chlorine.

In particular, the following substituted 1-arylpyrazoles of the general formula (I) may be mentioned in addition to the compounds mentioned in the preparation examples:

If, for example, 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-methylpyrazole and 1,1-difluoroethyl sulfen chloride are used as starting materials, the course of the reaction of process (a) according to the invention can be described by represent the following formula scheme:

The for carrying out the process (a) according to the invention as starting materials partially using or pyrazole derivatives of the formula (II) are known obtained by known processes (cf., for example, EP-A 295 117, EP-A 154 115, EP-A 201 852).

in welcher

R^3-1 und Ar

die oben angegebene Bedeutung haben,

können nach allgemein üblichen und bekannten Verfahren erhalten werden, wenn man Brommethyl-pyrazole der Formel (IIb),

in welcher

R^3-1 und Ar

die oben angegebene Bedeutung haben,

mit Alkalicyaniden, wie beispielsweise Natrium- oder Kaliumcyanid, gegebenenfalls in Gegenwart eines inerten Verdünnungsmittels, wie beispielsweise Wasser und in Gegenwart eines Phasentransferkatalysators, wie beispielsweise TEBA, bei Temperaturen zwischen 40°C und 100°C, vorzugsweise 70°C bis 100°C erhitzt (vgl. Herstellungsbeispiel).The pyrazole derivatives of the formula (IIa)

in which

R ^3-1 and Ar

have the meaning given above,

can be obtained by generally customary and known processes, if bromomethyl-pyrazoles of the formula (IIb)

in which

R ^3-1 and Ar

have the meaning given above,

with alkali metal cyanides, such as sodium or potassium cyanide, optionally in the presence of an inert diluent, such as water and in the presence of a phase transfer catalyst such as TEBA, at temperatures between 40 ° C and 100 ° C, preferably 70 ° C to 100 ° C heated (see production example).

If, for example, 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-bromomethylpyrazole is used as the starting material, an aqueous sodium cyanide solution and TEBA as the phase transfer catalyst, the reaction sequence of the process can be determined by the following equation represent:

in welcher

R^3-1 und Ar

die oben angegebene Bedeutung haben,

mit einer 48%-igen Bromwasserstoff-Eisessig-Lösung bei Temperaturen zwischen 60°C und 130°C, vorzugsweise bei Temperaturen zwischen 90°C und 130°C, erhitzt (vgl. Herstellungsbeispiele).The compounds of the formula (IIb) are obtained by generally customary and known processes if methoxymethyl-pyrazoles of the formula (IIc)

in which

R ^3-1 and Ar

have the meaning given above,

with a 48% hydrogen bromide-glacial acetic acid solution at temperatures between 60 ° C and 130 ° C, preferably at temperatures between 90 ° C and 130 ° C, heated (see Preparation Examples).

If, for example, 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-methoxypyrazole and 48% hydrogen bromide-glacial acetic acid solution are used as starting materials, the course of the reaction can be represented by the following formula scheme:

Ar

die oben angegebene Bedeutung hat mit

The compounds of the formula (IIc) can be obtained when arylhydrazines of the formula (X) Ar-NHNH ₂ in which

Ar

the meaning given above has with

gegebenenfalls in Gegenwart eines inerten organischen Lösungsmittels, wie beispielsweise Alkoholen, vorzugsweise Methanol, Ethanol oder Essigsäure oder Gemische aus Methanol-Essigsäure oder Ethanol-Essigsäure bei Temperaturen zwischen 50°C und 130°C, vorzugsweise 60°C und 120°C erhitzt. Zur Durchführung des Verfahrens setzt man pro Mol Arylhydrazin der Formel (X) im allgemeinen 1 bis 4 Mol, vorzugsweise 1 bis 2 Mol 1-Cyano-2-amino-3-methoxy-propen der Formel (XI) ein. Die Reaktionsführung, Aufarbeitung und Isolierung der Verbindungen der Formel (IVc) erfolgt in üblicher Art und Weise. 2-Amino-1-cyano-3-methoxy-propene of the formula (XI)

optionally in the presence of an inert organic solvent such as alcohols, preferably methanol, ethanol or acetic acid or mixtures of methanol-acetic acid or ethanol-acetic acid at temperatures between 50 ° C and 130 ° C, preferably 60 ° C and 120 ° C heated. To carry out the process, 1 to 4 moles, preferably 1 to 2 moles of 1-cyano-2-amino-3-methoxy-propene of the formula (XI) are generally employed per mole of arylhydrazine of the formula (X). The reaction, workup and isolation of the compounds of formula (IVc) is carried out in the usual manner.

If, for example, 2,6-dichloro-4-trifluoromethylphenylhydrazine and 1-cyano-2-amino-3-methoxy-propene are used as starting materials, the reaction course of the process can be represented by the following formula scheme:

The arylhydrazines of the formula (X) required as starting materials are general known compounds of organic chemistry.

2-amino-1-cyano-3-methoxy-propene of the formula (XI) is obtained when methoxyacetonitrile of the formula (XII) CH ₃ OCH ₂ -CN with acetonitrile and optionally in the presence of an inert organic solvent, such as, for example, ethers, preferably diethyl and dibutyl ether, glycol dimethyl ether and diglycol methyl ether, tetrahydrofuran and dioxane or from mixtures of acetonitrile with these solvents and in the presence of bases, such as, for example, sodium hydride or potassium tert. Butylate, at temperatures between 20 ° C and 150 ° C, preferably 20 ° C and 100 ° C, heated. For carrying out the process, methoxyacetonitrile, the corresponding base and acetonitrile are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reaction, workup and isolation of the compounds of formula (XI) is carried out in the usual manner (see Preparation Examples).

The compound of formula (XI) can be described as geometric isomers (E / Z isomers) or Isomer mixtures of different composition are present. In the following For the sake of simplicity, it is always the case of the compounds of the formulas (XI) although both the pure compounds and their mixtures with different proportions (E / Z isomers) are meant.

In addition, for carrying out the process (a) as starting materials required Sulfenylhalogenide are general by the formula (III) Are defined.

The sulfenyl halides of the formula (III) are generally known compounds of the organic chemistry.

For carrying out the process (b) required as starting materials 1-aryl-4-mercapto-pyrazoles are generally defined by the formula (Ia). In this formula (Ia), R ¹ , R ² , R ^3-1 and Ar are preferably those radicals and indices which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.

The compounds of the formula (Ia) are obtainable by process (a).

The 1-aryl-4-pyrazoles required as starting materials for carrying out the processes (c) and (d) are generally defined by the formula (Ic). In this formula (Ic), R ¹ , R ² , Ar and n are preferably those radicals and indices which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

The compounds of the formula (Ic) are obtainable by process (a) or (b).

The compounds also required as starting compounds of the formula (VII) are well known compounds of organic chemistry.

As nucleophiles (NuI) for carrying out the process (d) come all customary, suitable for such reactions reagents of the organic Chemistry in question. By way of example, but not by way of limitation: alcoholates, Hydrazine derivatives and cyanides.

As a diluent for carrying out the process (a) according to the invention are inert organic solvents in question. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, Hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ether, like Diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, Ketones such as acetone or butanone, nitriles such as acetonitrile or propionitrile; Amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters, such as ethyl acetate, Sulfoxides, such as dimethyl sulfoxide or acids, such as acetic acid.

If appropriate, the process (a) according to the invention can be carried out in the presence of a reaction auxiliary be performed. As such, all the usual inorganic ones come or organic bases. These include, for example, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as Sodium carbonate, potassium carbonate or sodium bicarbonate and tertiary Amines, such as triethylamine, N, N-dimethylaniline, pyridine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can in carrying out the inventive Method (a) can be varied over a wider range. In general works at temperatures between -20 ° C and + 120 ° C, preferably at temperatures between 0 ° C and + 50 ° C.

To carry out the process (a) according to the invention, the amount used per mole of the Pyrazole derivatives of the formula (II) generally 1.0 to 2.5 mol, preferably 1.0 to 1.5 moles of sulfenyl halide of formula (III) and optionally 1.0 to 2.5 Mole, preferably 1.0 to 1.5 moles of reaction auxiliaries. The reaction, Working up and isolation of the reaction products of the formula (Ia) takes place according to common methods.

As oxidizing agent for carrying out the process (b) according to the invention All the usual oxidizing agents which can be used for the oxidation of sulfur come question. Particularly suitable are hydrogen peroxide, organic peracids, such as for example, peracetic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid or Atmospheric oxygen.

As a diluent for carrying out the process (b) according to the invention inert inert organic solvents are also suitable. Preferably used Hydrocarbons, such as gasoline, benzene, toluene, hexane or petroleum ether; chlorinated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, chloroform, Carbon tetrachloride or chlorobenzene; Ethers, such as diethyl ether, dioxane or tetrahydrofuran; Carboxylic acids, such as acetic acid or propionic acid, or dipolar aprotic Solvents such as acetonitrile, acetone, ethyl acetate or dimethylformamide.

If appropriate, the process (b) according to the invention can be carried out in the presence of a Acid binder can be performed. As such, everyone usually comes usable organic and inorganic acid binder in question. Preferably one uses alkaline earth or alkali metal hydroxides, acetates or carbonates such as calcium hydroxide, sodium hydroxide, sodium acetate or sodium carbonate.

If appropriate, the process (b) according to the invention can be carried out in the presence of a suitable catalyst can be carried out. As such, everyone usually comes for such sulfur oxidation common metal salt catalysts question. As an example may be mentioned in this connection ammonium molybdate and sodium tungstate.

The reaction temperatures can in carrying out the inventive Method (b) can be varied within a substantial range. In general works at temperatures between -20 ° C and + 70 ° C, preferably at temperatures between 0 ° C and + 50 ° C.

To carry out the process (b) according to the invention, use is made of per mole of substituted 1-arylpyrazole of the formula (Ia) is generally 0.8 to 1.2 mol, preferably equimolar amounts of oxidizing agent, considering the oxidation of sulfur wants to interrupt on the sulphoxide stage. For the oxidation to the sulfone one sets pro Mol of substituted 1-arylpyrazole of the formula (Ia) generally 1.8 to 3.0 mol, preferably double molar amounts of oxidizing agent. The reaction procedure, Workup and isolation of the end products of the formula (Ib) is carried out according to usual procedures.

The active compounds are suitable for good plant tolerance and favorable warm-blooded toxicity for the control of animal pests, in particular insects, Arachnids and nematodes used in agriculture, forestry, storage and agriculture Material protection and on the hygiene sector occur. You can preferably used as pesticides. They are against normally sensitive and resistant Species as well as against all or individual stages of development. To the The above-mentioned pests include:

From the order of isopods e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of diplopoda e.g. Blaniulus guttulatus.

From the order of Chilopoda e.g. Geophilus carpophagus, Scutigera spec.

From the order of Symphyla e.g. Scutigerella immaculata.

From the order of Thysanura e.g. Lepisma saccharina.

From the order of Collembola e.g. Onychiurus armatus.

From the order of Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of Isoptera e.g. Reticulitermes spp ..

From the order of the Anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of Mallophaga e.g. Trichodectes spp., Damalinea spp.

From the order of Thysanoptera e.g. Herculothrips femoralis, Thrips tabaci.

From the order of Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp. Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the arachnids, e.g. Scorpio maurus, Latrodectus mactans.

From the order of Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

Plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..

The active compounds can be converted into the customary formulations, such as Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Active substance-impregnated natural and synthetic substances, very fine encapsulation in polymeric materials and in shell materials for seed, also in formulations with Fuel sets, such as smoked cartridges, doses, spirals, etc., as well as ULV cold and Warm mist formulations.

These formulations are prepared in a known manner, e.g. by mixing the active ingredients with extenders, ie liquid solvents, under pressure liquefied gases and / or solid carriers, optionally using of surface-active agents, ie emulsifiers and / or dispersants and / or foaming agents. In case of using water as Extenders can e.g. also organic solvents used as auxiliary solvents become. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as Water; with liquefied gaseous extenders or carriers are those Liquids meant which are at normal temperature and under normal pressure gaseous, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, Propane, nitrogen and carbon dioxide; as solid carriers there are suitable: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and ground synthetic minerals, such as fumed silica, alumina and silicates; as solid carriers for Granules are suitable: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifier and / or foaming agents are suitable: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, Arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

It can in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural Phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc are used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used in their commercial formulations as well as in the prepared from the formulations forms of application in mixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, Nematicides, fungicides, growth regulators or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, Carboxylic acid esters, chlorinated hydrocarbons, phenylureas, by microorganisms manufactured fabrics and others

Acrinathrin, Alphamethrin, Betacyfluthrin, Bifenthrin, Brofenprox, Cis-Resmethrin, Clocythrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Deltamethrin, Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Fluvalinate, Lambda-Cyhalothrin, Permethrin, Pyresmethrin, Pyrethrum, Silafluofen, Tralomethrin, Zetamethrin,

Alanycarb, Bendiocarb, Benfuracarb, Bufencarb, Butocarboxim, Carbaryl, Cartap, Ethiofencarb, Fenobucarb, Fenoxycarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Terbam, Thiodicarb, Thiofanox, Trimethacarb, XMC, Xylylcarb,

Acephate, Azinphos A, Azinphos M, Bromophos A, Cadusafos, Carbophenothion, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cyanophos. Demeton M, Demeton-S-methyl, Demeton S, Diazinon, Dichlorvos, Dicliphos, Dichlorfenthion, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Ethion, Etrimphos, Fenitrothion, Fenthion, Fonophos, Formothion, Heptenophos, Iprobenfos, Isazophos, Isoxathion, Phorate, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Methacrifos, Methamidophos, Naled, Omethoate, Oxydemeton M, Oxydeprofos, Parathion A, Parathion M, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamdon, Phoxim, Pirimiphos A, Pirimiphos M, Propaphos, Prothiophos, Prothoate, Pyraclophos, Pyridaphenthion, Quinalphos, Salithion, Sebufos, Sulfotep, Sulprofos, Tetrachlorvinphos, Temephos, Thiomethon, Thionazin, Trichlorfon, Triazophos, Vamidothion,

Buprofezin, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Pyriproxifen, Tebufenozide, Teflubenzuron, Triflumuron,

Imidacloprid, Nitenpyram, N-[(6-Chloro-3-pyridinyl)methyl]-N'-cyano-N-methylethanimidamid (NI-25),

Abamectin, Amitrazin, Avermectin, Azadirachtin, Bensultap, Bacillus thuringiensis, Cyromazine, Diafenthiuron, Emamectin, Ethofenprox, Fenpyrad, Fipronil, Flufenprox, Lufenuron, Metaldehyd, Milbemectin, Pymetrozine, Tebufenpyrad, Triazuron,

Aldicarb, Bendiocarb, Benfuracarb, Carbofuran, Carbosulfan, Chlorethoxyfos, Cloethocarb, Disulfoton, Ethophrophos, Etrimphos, Fenamiphos, Fipronil, Fonofos, Fosthiazate, Furathiocarb, HCH, Isazophos, Isofenphos, Methiocarb, Monocrotophos, Nitenpyram, Oxamyl, Phorate, Phoxim, Prothiofos, Pyrachlofos, Sebufos, Silafluofen, Tebupirimphos, Tefluthrin, Terbufos, Thiodicarb, Thiafenox,

Azocyclotin, Butylpyridaben, Clofentezine, Cyhexatin, Diafenthiuron, Diethion, Emamectin, Fenazaquin, Fenbutatin Oxide, Fenothiocarb, Fenpropathrin, Fenpyrad, Fenpyroximate, Fluazinam, Fluazuron, Flucycloxuron, Flufenoxuron, Fluvalinate, Fubfenprox, Hexythiazox, Ivemectin, Methidathion, Monocrotophos, Moxidectin, Naled, Phosalone, Profenofos, Pyraclofos, Pyridaben, Pyrimidifen, Tebufenpyrad, Thuringiensin, Triarathene sowie 4-Bromo-2-(4-chlorophenyl)-1-(ethoxsymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitril (AC 303630).

Mention may be made of the following compounds:

Acrinathrin, Alphamethrin, Betacyfluthrin, Bifenthrin, Brofenprox, Cis-Resmethrin, Clocythrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Deltamethrin, Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Fluvalinate, Lambda-Cyhalothrin, Permethrin, Pyresmethrin, Pyrethrum, Silafluofen, Tralomethrin, zetamethrin,

Alanycarb, Bendiocarb, Benfuracarb, Bufencarb, Butocarboxime, Carbaryl, Cartap, Ethiofencarb, Fenobucarb, Fenoxycarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Terbam, Thiodicarb, Thiofanox, Trimethacarb, XMC, Xylylcarb,

Acephate, Azinphos A, Azinphos M, Bromophos A, Cadusafos, Carbophenothion, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cyanophos. Demeton M, Demeton S-methyl, Demeton S, Diazinone, Dichlorvos, Dicliphos, Dichlorfthione, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxathione, Disulfoton, Edifenphos, Ethion, Etrimphos, Fenitrothion, Fenthion, Fonophos, Formothion, Heptenophos, Iprobenfos, Isazophos, Isoxathion, Phorate, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Methacrifos, Methamidophos, Naled, Omethoate, Oxydemeton M, Oxydeprofos, Parathion A, Parathion M, Phenthoate, Phorates, Phosalone, Phosmet, Phosphamdone, Phoxim, Pirimiphos A, Pirimiphos M, Propaphos , Prothiophos, prothoates, pyraclophos, pyridaphenthion, quinalphos, salithion, sebufos, sulfotep, sulprofos, tetrachlorvinphos, temephos, thiomethone, thionazine, trichlorfone, triazophos, vamidothion,

Buprofezin, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Pyriproxifen, Tebufenozide, Teflubenzuron, Triflumuron,

Imidacloprid, nitenpyram, N - [(6-chloro-3-pyridinyl) methyl] -N'-cyano-N-methylethanimidamide (NI-25),

Abamectin, Amitrazine, Avermectin, Azadirachtin, Bensultap, Bacillus thuringiensis, Cyromazine, Diafenthiuron, Emamectin, Ethofenprox, Fenpyrad, Fipronil, Flufenprox, Lufenuron, Metaldehyde, Milbemectin, Pymetrozine, Tebufenpyrad, Triazuron,

Aldicarb, Bendiocarb, Benfuracarb, Carbofuran, Carbosulfan, Chloroethoxyfos, Cloethocarb, Disulfone, Ethophrophos, Etrimphos, Fenamiphos, Fipronil, Fonofos, Fosthiazate, Furathiocarb, HCH, Isazophos, Isofenphos, Methiocarb, Monocrotophos, Nitenpyram, Oxamyl, Phorates, Phoxim, Prothiofos, Pyrachlofos, sebufos, silafluofen, tebupirimphos, tefluthrin, terbufos, thiodicarb, thiafenox,

Azocyclotine, butylpyridaben, clofentezine, cyhexatin, diafenthiuron, diethione, emamectin, fenazaquin, fenbutatin oxides, fenothiocarb, fenpropathrin, fenpyrad, fenpyroximate, fluazinam, fluazuron, flucycloxuron, flufenoxuron, fluvalinate, fubfenprox, hexythiazox, ivemectin, methidathione, monocrotophos, moxidectin, naled , Phosalone, Profenofos, Pyraclofos, Pyridaben, Pyrimidifen, Tebufenpyrad, Thuringiensin, Triarathene and 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (AC 303630).

The active compounds according to the invention can also be used in their commercial formulations as well as in the application forms prepared from these formulations Mixture with synergists. Synergists are compounds through which the Effect of the active ingredients is increased without the added synergist itself must be active.

The active substance content of the application forms prepared from the commercial formulations can vary widely. The drug concentration of Use forms may range from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1 wt .-% are.

The application is done in a custom forms adapted to the application forms Wise.

When used against hygiene and storage pests, the active ingredients are distinguished by an excellent Residualwirkung on wood and clay as well as by a good alkali stability.

Prozentangaben beziehen sich, wo nichts anders angegeben wird, auf Gewichtsprozente.

The preparation of the compounds of the formula (I) according to the invention will be illustrated by the following examples:

Percentages are by weight unless otherwise specified.

Preparation Examples Example 1:

(Process variant a)

15.5 g (0.05 mol) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-methyl-pyrazole are dissolved in 120 ml of absolute dichloromethane and 4.35 g (0.055 mol) of absolute Pyridine added. Then it is cooled to 0-5 ° C and added dropwise 7.3 g (0.055 mol) 1,1-Difluorethylsulfenchlorid to. It is stirred for 3 hours at 0 ° C and then overnight at room temperature. Then it is washed twice with water, dried with Magnesium sulfate and the solvent is removed in vacuo.

This gives 13.1 g (65% of theory) of 5-amino-3-methyl-4- (1,1-difluoroethylthio) -1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole of melting point 123-125 ° C.

Example 2:

(Process variant b)

4.6 g (0.0113 mol) of 5-amino-3-methyl-4- (1,1-difluoroethylthio) -1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole are heated in about 10 minutes at 25 ° C-35 ° C in 30 ml of 80% sulfuric acid. While cooling, 1 ml of 35% H ₂ O ₂ solution are added dropwise, then stirring is continued for 20 hours at room temperature. The reaction mixture is then diluted with water and the precipitate is filtered off with suction. After stirring with petroleum ether to obtain 1.8 g (38% of theory) of 5-amino-3-methyl-4- (1,1-difluoroethylsulfinyl) -1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole of melting point 177-179 ° C.

Analogously to Preparation Examples 1 and 2 and according to the stated processes (a) or (b), the following end products of the formula (I) can be obtained:

Example 15

(Process Variant d)

1.3 g (0.003 mol) of 5-amino-3-cyano-4- (1,1-difluoroethylthio) -1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole and 0.4 g (0.007 mol) of sodium methylate in 20 ml heated dry methanol for 6 hours under reflux. After that will be again 0.3 g (0.005 mol) of sodium methylate was added and refluxed for a further 10 hours heated. After removal of the solvent in vacuo, the remaining The residue is stirred with water and filtered with suction. The precipitation is repeated several times washed with water and dried.

This gives 1.1 g (85% of theory) of 5-amino-3-cyano-4- (1,1-difluoroethylthio) -1- (2-chloro-4-trifluoromethyl-6-methoxyphenyl) pyrazole of melting point 79 ° C.

Example 16

0.7 g (1.7 mmol) of 5-amino-1- (2-chloro-6-fluoro-4-trifluoromethylphenyl) -3-methoxymethyl-4- (1,1-difluoroethylthio) pyrazole and 1g (6.54 mmol) of tetraethylammonium cyanide are dissolved in 5 ml of anhydrous dimethylformamide and 18 hours at stirred at about 100-110 ° C. For work-up, it is poured into 100 ml of water and filtered off with suction from the resulting solid. After repeated washing with water to obtain 0.45 g (63% of theory) of 5-amino-1- (2-chloro-6-cyano-4-trifluoromethyl) -3-methoxymethyl-4- (1,1-difluoroethylthio) pyrazole as ocher-colored solid from Melting point 84 ° C.

Example 17

9 g (0.022 mol) of 5-amino-1- (2-chloro-4-trifluoromethylpyridyl) -3-methoxymethyl-4- (1,1-difluoroethylthio) pyrazole are added at 0 ° C with 18 ml of water and 18 ml of conc , Sulfuric acid added. At 0 ° C, a solution of 2.3 g (0.033 mol) of sodium nitrite and 10 ml of water is added dropwise in about 30 minutes. After addition of 0.5 g of urea are added dropwise at 0 ° C 27 ml (0.261 mol) of hypophosphorous acid (50% aqueous solution). Thereafter, stirring is continued for 18 h at room temperature. After the addition of potassium carbonate, the alkaline solution is extracted with dichloromethane. The combined dichloromethane phases are concentrated after drying over MgSO ₄ in vacuo. The remaining oil is then distilled in a bulb tube. At 180 ° C / 0.1 mm, 4.2 g (48% of theory) of 1- (2-chloro-4-trifluoromethylpyridyl) -3-methoxymethyl-4- (1,1,1-difluoroethylthio) pyrazole are obtained as an orange oil.

Analogously to Preparation Examples 15 to 17 and according to the stated processes (c) and (d), the following end products of the formula (I) can be obtained:

Preparation of the starting compounds Example (II-1)

37 g (151 mmol) of 2,6-dichloro-4-trifluoromethylphenylhydrazine and 4.9 g (438 mmol) 1-cyano-2-amino-3-methoxy-propene in 300 ml of ethanol and 20 ml of acetic acid Heated under reflux for 24 hours. Then again 12g (49 mmol) Added 2,6-dichloro-4-trifluoromethylphenylhydrazine and for a further 24 hours heated to reflux. Then the solvent is removed in vacuo, the residue is purified by column chromatography (silica gel, mobile phase: cyclohexane / Ethyl acetate 1: 1).

This gives 48.4 g (71% of theory) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-methoxy-methyl-pyrazole as oil.

¹ H NMR δ *) = 7.7 ppm (s, 2H); 5.74ppm (s, 1H); 4,42ppm (s, 2H); 3.4ppm (s, 3H).

To 21.5 g (0.19 mol) of potassium tert-butoxide in 250 ml of dry tetrahydrofuran A solution of 15 g (0.21 mol) of methoxyacetonitrile is added dropwise in about 30 minutes and 10 g (0.24 mol) of acetonitrile in 50 ml of dry tetrahydrofuran. After finished The addition is heated under reflux for a further 24 hours. After careful Hydrolysis with water is extracted with dichloromethane. The United organic phases are dried after drying over magnesium sulfate in vacuo concentrated. The subsequent fractional distillation gives at 80 ° C / 0.2 mm 8.9g (38% of theory) of 2-amino-1-cyano-3-methoxypropene as an orange oil.

From the ¹³ C NMR data results in a ratio of the E / Z isomers of 1: 4.

Example (II-2):

In an analogous manner, from 2-chloro-6-fluoro-4-trifluoromethylphenyl-hydrazine and 2-Amino-1-cyano-3-methoxy-propene 5-Amino-1- (2-chloro-6-fluoro-4-trifluoromethylphenyl) -3-methoxymethylpyrazole receive.

Example (II-3):

In an analogous manner is from 2-chloro-4-trifluoromethylpyridyl-hydrazine and 2-amino-1-cyano-3-methoxypropene 5-Amino-1- (2-chloro-4-trifluoromethylpyridyl) -3-methoxymethyl-pyrazol obtained as an oil.

¹ H NMR δ *) = 8.6 ppm (d, 1H); 8.13ppm (d, 1H); 5.67ppm (s, 1H); 4.8ppm (bs, NH ₂ ); 4.41 ppm (s, 2H); 3.4ppm (s, 3H).

Example (II-4):

1.5 g (4.4 mmol) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-methoxymethyl-pyrazole are dissolved in a mixture of 30 ml of 48% HBr and 15 ml of acetic acid heated to 120-130 ° C for about 8 hours. The reaction mixture is in Concentrated vacuum and then stirred with dilute ammonia solution. Of the brown solid is filtered off with suction and washed several times with water.

This gives 1.6 g (93% of theory) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-bromomethylpyrazole of melting point 220 ° C.

Example (II-5):

In an analogous manner, this is prepared from 5-amino-1- (2-chloro-4-trifluoromethylpyridyl) -3-methoxymethyl-pyrazole and 48% HBr and acetic acid 5-amino-1- (2-chloro-4-trifluoromethylpyridyl) -3-bromomethyl-pyrazole receive.

Example (II-6):

5 g (12.9 mmol) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-bromomethylpyrazole are treated with 2.5 g (51 mmol) of sodium cyanide in 30 ml of water in the presence of 4 g (17.6 mmol) triethylbenzylammonium chloride at 90 ° C for 18 hours. It is cooled to about 5 ° C and sucks off the gray solid. Chromatography on silica gel 60 (eluent: methylene chloride / ethanol 1: 1) gives 1.7 g (40% of theory) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyanomethyl-pyrazole as a brown solid of melting point 98 ° C.
_* ) The ¹ H NMR spectra were recorded in deuterochloroform (CDCl ₃ ) with tetramethylsilane (TMS) as internal standard. The chemical shift is given as the δ value in ppm.
_** ) The ¹ H NMR spectra were recorded in deuterated dimethylsulfoxide ((CD ₃ ) ₂ SO) with tetramethylsilane (TMS) as internal standard. The chemical shift is given as the δ value in ppm.

applications

5-Amino-1-[2,6-dichlor-4-(trifluormethyl)-phenyl]-4-[(trimethyl)-sulfinyl]-3-cyano-1H-pyrazol
(bekannt aus EP-A 295 117) In the following application examples, the following compound is used as reference substance:

5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4 - [(trimethyl) sulfinyl] -3-cyano-1H-pyrazol
(known from EP-A 295 117)

Example A

Myzus Test solvent 7 parts by weight dimethylformamide emulsifier 1 part by weight Alkylarylpolyglykolether

To prepare a suitable preparation of active compound, 1 Part by weight of active compound with the stated amount of solvent and the indicated Amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) growing heavily from the peach aphid (Myzus persicae) are infested by dipping into the preparation of the active ingredient Concentration treated.

After the desired time the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids killed were.

In this test, e.g. the following compounds of Preparation Examples 1 and 5 superior efficacy over the prior art (kill rate 0%), with a kill rate between 98% and 100% at drug concentration of 0.1% after one day.

Example B

Aphis test (systemic effect) solvent 7 parts by weight dimethylformamide emulsifier 1 part by weight Alkylarylpolyglykolether

To prepare a suitable preparation of active compound, 1 part by weight is mixed Active substance with the stated amount of solvent and the specified Amount emulsifier and dilute the concentrate with water to the desired Concentration.

With 20 ml of active compound preparation of the desired concentration bean plants (Vicia faba), heavily infested by the black bean louse (Aphis fabae) are soaked, so that the active ingredient preparation penetrates into the soil, without the To wet scion. The active ingredient is absorbed by the roots and into the Sprout forwarded.

After the desired time the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids killed were.

In this test, e.g. the following compounds of Preparation Examples 1 and 5 superior efficacy over the prior art (kill rate 0%), with a kill rate between 90% and 100% at the same drug concentration of 0.02% after four days.

Example C

Limit concentration test / root systemic effect test insect Phaedon cochleariae larvae solvent 3 parts by weight of acetone emulsifier 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight is mixed Active substance with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired Concentration.

The preparation of active compound is intimately mixed with soil. It plays the concentration of the active substance in the preparation practically does not matter, is crucial only the weight of active substance per unit volume of soil, which is in ppm (= mg / l). The treated soil is filled into pots and planted this with cabbage (Brassica oleracea). The active ingredient can be so from the plant roots taken from the ground and transported into the leaves.

For proof of the root-systemic effect become exclusive after 7 days the leaves are occupied with the above test animals. After another 2 Days is the evaluation by counting or estimating the dead animals. From the Killing rates are derived from the root systemic effects of the drug. she is 100% if all the test animals are killed and 0%, if just as many Test insects live as in the untreated control.

In this test, e.g. the following compounds of Preparation Examples 1, 5 and 18 superior efficiency over the prior art (kill rate 0%), with a kill rate of 100% in each drug group filtration of 2.5 ppm.

Example D

Limit concentration test / root systemic effect test insect Myzus persicae solvent 3 parts by weight of acetone emulsifier 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight is mixed Active substance with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired Concentration.

The preparation of active compound is intimately mixed with soil. It plays the concentration of the active substance in the preparation practically does not matter, is crucial only the weight of active substance per unit volume of soil, which is in ppm (= mg / l). The treated soil is filled into pots and planted this with cabbage (Brassica oleracea). The active ingredient can be so from the plant roots taken from the ground and transported into the leaves.

For proof of the root-systemic effect become exclusive after 7 days the leaves are occupied with the above test animals. After another 2 Days is the evaluation by counting or estimating the dead animals. From the Killing rates are derived from the root systemic effects of the drug. she is 100% if all test animals are killed and 0%, if just as many Test insects live as in the untreated control.

In this test, e.g. the compound 5 of the preparation example a Kill rate of 100% over the prior art (kill rate 0%) at a drug concentration of 20 ppm.

Example: E

Blowfly larvae test test animals Lucilia cuprina larvae emulsifier 35 parts by weight of ethylene glycol monomethyl ether
35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable preparation of active compound, three are mixed Parts by weight of active ingredient with seven parts by weight of the mixture indicated above and dilute the emulsion concentrate thus obtained with water to each desired concentration.

Approximately 20 Lucilia cuprina res.-larvae are placed in a test tube containing about 1 cm ³ horse meat and 0.5 ml of the active ingredient preparation. After 24 hours, the effectiveness of the preparation of the active ingredient is determined. 100% means that all Blowfly larvae have been killed; 0% means that no Blowfly larvae have been killed.

In this test, e.g. the following compounds of Preparation Examples 4 and 12 killing effect at 100% at a drug concentration ≥ 300 ppm compared to the prior art, this effect only at a Drug concentration of 1000 ppm achieved.

Example F

flying test test animals Musca domestica, strain WHO (N) solvent 35 parts by weight of ethylene glycol monomethyl ether
35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable formulation, mix three Parts by weight of active compound with seven parts of the abovementioned solvent / emulsifier mixture and dilute the emulsion concentrate thus obtained with water the particular desired concentration.

2 ml of this preparation of active ingredient are placed on filter paper discs (⊘ 9.5 cm) Pipetted, which are located in Petri dishes of appropriate size. After drying the filter discs, 25 test animals are transferred to the petri dish and covered. After 6 hours, the effectiveness of the preparation of the active ingredient is determined. The effectiveness you express in%. 100% means that all flies are killed were; 0% means that no flies have been killed.

In this test, e.g. the compound of Production Example 5 is superior Effect (100% kill) at a drug concentration of 1 ppm, over the prior art (<100%).

Example G

cockroach test test animals Blattella germanica or Periplaneta americana solvent 35 parts by weight of ethylene glycol monomethyl ether
35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable formulation, mix three Parts by weight of active compound with seven parts of the abovementioned solvent / emulsifier mixture and dilute the emulsion concentrate thus obtained with water the particular desired concentration.

2 ml of this preparation of active ingredient are placed on filter paper discs (⊘ 9.5 cm) Pipetted, which are located in Petri dishes of appropriate size. After drying of the filter discs become 5 test animals in Blattelle germanica or Periplaneta americana transferred to the petri dish and covered.

After 6 hours, the effectiveness of the preparation of the active ingredient is determined. The effectiveness you express in%. 100% means that all flies are killed were; 0% means that no flies have been killed.

In this test, e.g. the compound of Production Example 1 is superior Effect (100% kill> 10 ppm drug concentration) over the State of the art (kill rate <100% at 10 ppm active ingredient concentration).

Example H

In vitro test for fleas (all stages of development) test object All stages (eggs, larvae, pupae and adults) of Ctenocephalides felis. test method Blood meal is dried overnight in a shallow dish at about 70 ° C and then sieved with a mesh size of 0.63 mm. Each 1.8 g of the prepared blood meal are placed in plastic Petri dishes of 9.8 cm ⊘. 0.2 ml of the substance is added to the 1.8 g blood meal with the Eppendorf pipette (dilution 1:10). That at 1 ppm application concentration, the aqueous solution must have a concentration of 10 ppm. The application of the solution is done dropwise over the entire surface of the blood meal. Allow the skins to dry overnight. With a suitable device, the substance, which is now present in dried blood meal lumps, crushed and distributed by rotating movements homogeneously in the Petri dish. A spatula tip of screened flea eggs (derived from artificially infected cats) is now placed in the prepared test dishes. The dish is closed with Parafilm and shaken vigorously. The incubation takes place at 25 ° C and 85% relative humidity. The shells are examined at certain intervals for stages of development of the fleas. test criteria Criteria for the in vitro action of a substance are the inhibition of the development of the flies, or a developmental standstill before the adult stage. rating Effective: After 1 1/2 fold development time, no adult fleas appear. Ineffective After a 1/2-fold developmental period, adult fleas appear.

In this test, e.g. the compound of Preparation Example 4 a clear superior effect (100% kill already at 1 ppm active ingredient concentration) over the prior art (0% kill at 10% drug concentration).

Claims (7)

1. Substituted 1-arylpyrazoles of the general formula (I)

   

   in which

   R¹

   represents hydrogen, cyano, (C₁-C₄)-alkyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, trifluoromethyl, bromomethyl and cyanomethyl,

   R²

   represents 1,1-difluoroethyl,

   R³

   represents amino or the following group

   

   in which

   R⁵

   represents hydrogen or (C₁-C₄)-alkyl,

   R⁶

   represents phenyl,

   Ar

   represents phenyl which is disubstituted or trisubstituted by identical or different substituents, where the 2-position is occupied by fluorine or chlorine, the 4-position by trifluoromethyl and the 6-position by fluorine, chlorine, cyano, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, or

   Ar

   represents a 2-pyridyl radical which is substituted in the 5-position by trifluoromethyl and in the 3-position by fluorine or chlorine, and

   n

   represents a number 0, 1 or 2.

2. Process for the preparation of substituted 1-arylpyrazoles according to Claim 1, characterized in that

   a) substituted 1-aryl-4-mercapto-pyrazoles of the formula (Ia)

   

   in which

   R¹, R² and Ar

   have the meanings given in Claim 1 and

   R^3-1

   represents amino

   are obtained when
   pyrazole derivatives of the formula (II)

   

   in which
   R¹, R^3-1 and Ar have the abovementioned meanings,
   are reacted with sulphenyl halides of the formula (III) R²-S-Hal in which

   R²

   has the abovementioned meaning and

   Hal

   represents halogen, in particular chlorine or bromine,

   if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or

   b) in that substituted 1-arylpyrazoles of the formula (Ib)

   

   in which
   R¹, R², R^3-1 and Ar have the abovementioned meanings and
   n represents the number 1 or 2
   are obtained when compounds of the formula (Ia)

   

   in which
   R¹, R² and R^3-1 and Ar have the abovementioned meanings

   are oxidized using oxidants, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst.
3. Pesticides, characterized in that they contain at least one 1-arylpyrazole according to Claim 1.
4. Method of combating animal pests, in particular insects, characterized in that 1-arylpyrazoles according to Claim 1 are allowed to act on animal pests and/or their environment.
5. Use of 1-arylpyrazoles according to Claim 1 for combating animal pests, in particular insects.
6. Insecticidal compositions, characterized in that they contain at least one 1-arylpyrazole according to Claim 1.
7. Process for the preparation of compositions against animal pests, characterized in that 1-arylpyrazoles according to Claim 1 are mixed with extenders and/or surface-active agents.